A thermogravimetric method based on dynamic heating and the use of an internal source of SO2 (metal sulfates with a suitable range of decomposition temperatures) was used to compare the SO2-binding abilities of various lime-containing materials.
By means of this method, furnace and cyclone ashes formed in the combustion of oil-shale in the Baltic Power Station, their
differently activated (grinding, hydrating) forms and some carbonaceous materials were investigated to estimate their suitability
for exhaust gas purification in thermal power stations.
The dynamics of SO2 emission during thermooxidation of Estonian oil shale, its semicoke, different samples of coal and their mixtures, as well
as the influence of Estonian oil shale ash addition (for modelling the CFBC process) on the dynamics were studied. The experiments
were carried out with thermogravimetric equipment under dynamic heating conditions (5 K min-1) in the atmosphere of dried air, with simultaneous gastitrimetric EGA.
It was established that SO2 emission from the fuels started at 200-320C. Depending on the form of sulphur (organic, pyritic, sulphate), the emission
took place in two or three steps, and continued up to 580-650C, during which 35-75% of the total sulphur was emitted into
the gaseous phase. Regulating the mole ratio of free CaO/S in the mixtures of fuels with oil shale ash addition the emission
of SO2 ceased abruptly at 460-540C and it was limited to the level of 7-30%.
Ammonium nitrate (AN) is one of the main nitrogen fertilizers used in fertilization programs. However, AN has some serious
disadvantages — being well soluble in water hardly 50% of the N-species contained are assimilated by plants. The second disadvantage
of AN is associated with its explosive properties. The aim of this paper was to clarify the influence of different lime-containing
substances — mainly Estonian limestone and dolomite — as internal additives on thermal behaviour of AN.
Commercial fertilizer grade AN was under investigation. The amount of additives used was 5, 10 or 20 mass%, or calculated
on the mole ratio of AN/(CaO, MgO)=2:1 in the blends. Experiments were carried out under dynamic heating condition up to 900°C
(10°C min−1) in a stream of dry air or N2 by using Setaram Labsys 2000 equipment coupled to Fourier transform infrared spectrometer (FTIR).
The results of analyses of the gaseous compounds evolved at thermal treatment of neat AN indicated some differences in the
decomposition of AN in air or in N2. At the thermal treatment of AN’s blends with CaCO3, MgCO3, limestone and dolomite samples the decomposition of AN proceeds through a completely different mechanism — depending on
the origin and the content of additives, partially or completely, through the formation of Mg(NO3)2 and Ca(NO3)2.
The results obtained by studying decarbonization of different samples of Estonian limestone and dolomite and the following
sulphation or carbonation of calcined products to estimate their SO2 and CO2 binding ability were presented. Experiments were
carried out with thermogravimetric equipment(Q-Derivatograph, MOM and Labsys™, SETARAM) – calcination of the samples in the
atmosphere of air with the heating rate 10 K per minute using multiplate crucibles, the following sulphation or carbonation
of the calcined products after cooling to the fixed temperature (temperature range 400–900C) under isothermal conditions
in the flow of air-SO2 or air-CO2 mixture. Chemical, X-ray, BET nitrogen dynamic desorption, etc. methods for the characterization of the initial samples,
intermediate and final products were used.
In addition, the possibilities of recurrent use of oil shale ashes taken from different technological points at operating
thermal power plants (Estonian and Baltic TTPs, Estonia) as sorbents for SO2 binding from gaseous phase were studied, as well as the possibilities of activation of these ashes towards SO2 binding.
The results of these studies confirmed the high reactivity of Estonian limestone and dolomite towards SO2 and CO2. Dependence of SO2 binding mechanism on the SO2 concentration has been established. Modelling of SO2 capture of dolomite and limestone was carried out to establish the kinetic parameters of these processes. The possibilities
of activation of oil shale ashes and their effective recurrent use for binding SO2 and CO2 from gaseous phase were confirmed.
Approximately one million tons of semicoke (SC) is formed and stored in open air dumps every year in the production of shale
oil by processing Estonian oil shale (OS). The content of different harmful compounds as sulphides, PAH, phenols, etc. in
SC make these dumps one of the most serious sources of environmental contamination. The aim of this work was to study the
behaviour of sulphur compounds in OS and its SC, formation of SO2 and possibilities of binding it into the solid phase during thermooxidation of fuel blends based on SC. Blends modified with
SC ash addition were studied as well. It was determined that SO2 emission in thermooxidation of SC samples started at 280-300C and proceeded with a steady speed up to 580-600C and the
amount of sulphur evolved was 5-10% from the total content of sulphur in the sample. The amount of SO2 emitted decreased depending on the mass ratio of the composite fuels from 49-56 to 15-35% during thermooxidation of OS samples
studied or their blends with SC, respectively, from 43-80% for coal samples to 13-60% for their blends with SC and to 2-13%
during thermooxidation of these blends modified with SC ash addition. In the products of thermooxidation formed at 800-900C
the only sulphur containing phase was CaSO4, at 650C also traces of CaS and CaMg3(SO4)4 were fixed.
Authors:T. Kaljuvee, A. Trikkel, R. Kuusik, and V. Bender
Summary The results of investigation of MgO participation in the binding of SO2 with lime-containing materials as sorbents are presented. Experiments of SO2 binding into solid phase using model samples of reactive grade MgO and CaO varying the mole ratio of MgO/CaO from 9:1 to 1:9 were carried out. Besides, dolomite and limestone samples with different MgO/CaO mole ratio (from 1.24 to 0.13) and samples of ashes formed at combustion of Estonian oil shale (containing 35-40% of carbonates) and its semicoke were studied Initial samples, intermediate and final products were subjected to chemical, IR-spectroscopy, X-ray and BET specific surface area analyses. The results of the present study confirmed the active participation of MgO in the binding of SO2 into the solid phase. In addition to CaSO4 the formation of Ca,Mg-double sulphate CaMg3(SO4)4 and ß-MgSO4 was observed. The presence of CaMg3(SO4)4 was fixed in a large temperature range 400-900°C and that of ß-MgSO4 in between 500-700°C. The optimum temperature range for formation and durability of CaMg3(SO4)4 was 700-800°C.
Authors:T. Kaljuvee, M. Toom, A. Trikkel, and R. Kuusik
The extensive use of fossil fuels in energy production causes serious
pollution of atmosphere with SO2, CO2,
NOx, etc. In Estonia the electricity production is
based mainly on the pulverized firing (PF) of low-grade local fuel –
Estonian oil shale (EOS) which is characterized by a low calorific value (~9
MJ kg–1) and a high content of mineral matter
(65–70%) from which approximately 50% are carbonates. Since 2004, also
two boilers based on circulating fluidized bed combustion (CFBC) of EOS are
The present study is focused on the comparative
investigation of the efficiency of different ashes collected from different
technological points of CFB and PF boilers as sorbents for SO2.
The influence of experimental temperature on the SO2-binding
characteristics of ashes as well as the possibilities of activation of ashes
(grinding, hydration) were investigated. It was shown that the SO2-binding
capacity of initial ashes at 700C and p(SO2)=190
mm Hg was for CFBC ashes 24–30 mg and for PF ashes 10–23 mg SO2
per 100 mg sample, the best binding capacities belonging to economizer ash
(ECOA) and electrostatic precipitator ash from the 1st field (PESPA1f), respectively.
However, during initial stage of binding the best results were obtained with
air pre-heater ash (PHAA) and ESPA1f (both CFBC ashes). Grinding improved
the SO2-binding ability, being the most effective in
the case of bottom ash (BA) from CFBC and cyclone ash (PCA) from PF –
increase in binding capacity 2 and 2.3 times, respectively. As compared to
initial CFBC ashes, the binding characteristics of PF ashes remained lower
even after grinding. Hydration and previous calcination improved the binding
characteristics only of PF ashes. Hereby, the SO2-binding
ability of CFBC ashes is better than of PF ashes and they are more promising
sorbents for acidic gases, for example, for sulphur dioxide.
Authors:I. Klimova, T. Kaljuvee, L. Türn, V. Bender, A. Trikkel, and R. Kuusik
In order to elucidate the influence of Ca and Mg carbonates with or without the presence of boron, manganese and copper compounds on the thermal stability of ammonium nitrate (AN), thermodynamic analysis of different reactions between AN and additives was carried out. Temperature dependency of Gibbs free energy changes ΔGT and equilibrium composition of reaction products were calculated for a set of reactions using the HSC software. Main solid compounds that can form in the systems of AN and carbonates, were Ca(NO3)2 and Mg(NO3)2, Ca(OH)2 and Mg(OH)2, CaO2 and MgO2, CaO and MgO, and N-containing gaseous compounds NO, N2O and NO2. As a result of H3BO3, MnO2 and CuSO4 addition, the content of CuO, Cu2O and MnO as solids and SO2, SO3 and HBO as gaseous reaction products reached the same level. Thereby, their equilibrium concentrations did not depend on the carbonate origin of CaCO3, MgCO3 or CaMg(CO3)2. Small amount of CuSO4, H3BO3 or MnO2 additive (0.01–0.05 mol) in the system, practically, did not influence the temperature dependencies of ΔGT of the reactions between AN and CaCO3 or CaMg(CO3)2. The influence of additives taken in the larger amount (0.5 mol) was evident and, depending on the additive and reaction, shifted their proceeding temperatures in either direction by more than 300–400 K.